Process for the manufacture of chlorinated phenol esters and of oxybenzyl alcohols, oxybenzaldehydes, and oxybenzoic acids.



unrrn MANY, ASSIGNORS TO FRIEDRICH RASCHIG, OF LUDWIGSHAFEN-ON-THE-RHINE,

GERMANY.

PROCESS FOR THE MANUFACTURE OF CHLORINATED PHENOL ESTERS AND OF OXYBENZYL ALCOHOLS, OXYBENZALDEHYDES, AND OXYBENZOIC ACIDS l ,4l23,'?5. No Drawing.

To all whom, it may concern:

Be it known that we, FRIEDRICH RASCIITG and MAX Kt'mnnn, manufacturing chemists, subjects of the German Emperor. esiding" at Ludwigshafen-on-the-Rhinc. Germany, have invented certain new and useful improvements in processes for the manufacture of chlorinated phenol esters and ot oxybcnzyl alcohols, oxybcnzaldehydes, and oxybenzoic acids, of which the following is a specification.

vIt phenols having side-chains, such as cresols and Xylenols, are treated with chlorin or other chlorinating'media, the chlorin, according to the observations hitherto made, will usually enter the benzene nucleus. We have found, that the chlorin .will completely 'or almost completclyentcr the side chains,

inorganic or organic acid residues are introduced into the hydroxyl group of the phenol. Spec1ally suitable for this purpose are the esters of carbonic and of phosphoric acid, which can be easily produced from phosgcne or phosphorus-oxychlorid and the corresponding phenols. The same result may be obtained by introducing the radical of the phosphorus acid or of the benzene-sub ionic acid or of an alphyl-sulfonic acid. The esters are melted in an enameled or lead-lined receptacle and heated to a temperature between 150 to 180. Into this liquid is introduced chlorin, which has a substituting' effect on the hydrogen atoms of the methyl groups, 1, 2 or 3 hydrogen atoms of the methyl group being gradually re placed by chlorin, according to the quantity introduced, while the corresponding quantity of hydrochloric acid escapes. In this manner the esters of substituted ,benzyL chlorids, benzal chlorids and benzotrichlorids may be obtained, which are intended to be used in the dyeing industry, perfumery and pharmacy. The principal importance of'the present process, however,consists in the fact, that by the saponification of these chlorination products, the same being boiled in alcoholic solution with caustic soda the alcohol distilled oil and acid added for the purpose of binding the soda, oxyhenzyl alcohols, oxybenzaldehydes and oxybcn- Specification of Letters Patent. Application filed. May 15, 1909. Serial No. 496,300.

Patent-ed Apr. Mi, 19112.

viding a simple method of deriving these products from easily available and cheap cresols, xylenols and similar materials.

The conversion ofthc chlorinated esters into alcohols, aldehydes. acids during saponificatio'n takes place, for instance, in the manner lndicated by the following equations:

Oxybenzylidene ChlOl'lll Oxybenzaldehyde.

carbon ate.

.uct to cool, W-monochlor-o-cresol-carbonic acid ester i [-Q-co-O-I is obtained. It is boiled with water and an excess of calcuun carbonate at 45 atmos- CIiIgCl pheres pressure, whereby at the same time carbonic acid is split oil and the chlorin is replaced by the hydroXyl-group. From the solution filtered off the calcium carbonate, the o-oxybenzyl-alcohol crystallizes out.

' Example I: 242 kilograms of orthocresolcarbonate are treated with chlorin gas at 180 C. until an increase of weight amounting to 138 kilograms has taken place. The result is a thick oil, which at the pressure of 30 millimeters mercury column may be distilled at 247 C. and the principal part of which consists of dicl1lororthocresol-carbonic acid ester. The reaction takes place according to the following equation:

4. Ortbo-crcsol-carbonatc.

011 complete (exhaustive) saponification it yields salicylic-aldehyde about 80% of the theoretical quantity.

Example II: 242 kilograms of paracresolcarbonate are treated with chlorin, as described in Example I. The reaction takes place according to the following example:

' laracresolenrbonate.

Example IV: 368 kilograms of orthocresol-phosphate boiling of phosphorus-oxychlorid (one molecular proportion) and ortho-cresol (three molecular proportions) are treated with chlorin at 160 to 180 C. until the Weight has increased by 207 kilos. The reaction hours.

takes place according to the equation:

The oil obtained in this manner yields on saponification about 50 per cent. of the theoretically aldehyde.

Example V: For the manufacture of ortho-cresol-phosphorous acid ester 324 kilos of ortho-cresol are mixed with 137.5 kilos of phosphorus trichlorid. The formation of the ester takes place at first spontaneously, while liberating hydrochloric acid and is continued'by heating to 180 for about two As soon as the escape of hydrochloric acid ceases, thereaction is completod. Into the ester obtained chlorin is introduced. At first a separation of crystals will be noticed, owing to the formation of an additive compound viz:-tricresylphosp'hate-chlorid CH .d II O) P01 This product, however, is soon melted by the heat of the reaction, whereupon chlorin is admitted at a temperature of 150 to 180 C. until the weight has increased by 93 kilos. The result is a thick oil consisting mainly of ortho-oxybenzylidene chlorid-phosphatechlorid (CHCl .C H O) ,PCl and yielding on saponification salicylic-aldehyde about 50% of tlfe theoretical quantity. The transobtained by prolonged" possible quantity of sa1icylic-' format-ion takes place according to the equa-,

CuHaSOz.O.C6H4.CHa+2Clz=CaHaElOz.O.CaH4. lHCl:+2l-ICL The resulting oil, consisting largely of the benzene-sulfonic acid ester of ortho-oxyben-' zylidene-chlorid, yields on exhaustive saponification salicylic aldehyde, about 80% .of the theoretical quantity.

Example VII, (manufacture of salicylic aldehydez) 192 kilograms of ortho-oxybenzylidene-chlorid-phosphoric acid ester are dissolved in 2,000 liters of alcohol and boiled with a concentrated aqueous solution of 160 kilos of caustic soda for a quarter of an hour on the reflux-cooler. The saponification takes place according to the equation:

After the alcohol has been distilled oil, the

sodium compound of salicylic aldehyde is decomposed by an excess of sulfuric acid and the salicylic aldehyde is distilled off with steam.

-What we claim is e e 1. The process for the manufacture of phenols oxidized in the side chain, which consists in treating the acid-esters of the homologues of phenof'with a chlorinating agent at an increased temperature, and causing saponifying agents to act on the phenol-esters thus obtained and chlorinated in the aliphatic side-chain.

2. The process for the manufacture of phenol-esters chlorinated in the side-chain, which consists in introducing an acid-radical into the hydroxyl group of the said phenol and treating the ester thus produced with chlorin.

3. The process for the manufacture of phenol-esters chlorinated in the side-chain, which consists in introducing an acid-radical into the hydroxyl group of the said phenol,

melting the ester thus produced and treating it with a chlorin at an increased temperature.

4. The process for the manufacture of phenol-esters chlorinated in the side-chain, which consists in introducing an acid-radical into the hydroxyl group of the said phenol, melting the ester thus produced and treating 1t with chlorin at a temperature of 150 to 180 C. until the desired increase of weight has been produced.

5. The process for obtaining chemical compounds from phenols having side-chains,

which consists in introducing an acid-radical into the hydroxyl group of the said phenol, treating the ester thus produced with chlorin and s'aponifying the product.

6. lhe process for obtaining chemical compounds from phenols having side-chains, which consistsin introducing an acid-radical into the hydroxyl group of the said phenol, melting the ester thus produced, treating itwith chlorin at an increased temperature and saponifyingthe product.

7. The process for obtaining chemical compounds from phenols having side-chains,

Which consists in introducing an acid-radical into the hydroxyl group of the said phenol, melting the ester thus produced and treating it with chlorin at a temperature of 150 to 180 C. untilthe desired increase of weight has been produced and saponifying the product of chlorination, substantially as described. A.

In testimony whereof we have hereunto set our'hands in presence of two subscribing witnesses.

FRIEDRICH RASOHIG.

MAX KoBNER.

Witnesses:

I Ronnm: GERLACH,

A. T. MITTON. 

